KR102476505B1 - Performance enhancing additives for fuel compositions and methods of use thereof - Google Patents

Abstract

In one embodiment, the present invention provides (i) an acid amide; and ( ii) a derivative of an oxide-treated amine; and (ii) a mixture or blend of a derivative of an oxide-treated amine, and further comprising a detergent, in another embodiment a fuel composition thereof, and in another embodiment a method of use thereof. , and, in another embodiment, to a method of improving fuel and engine performance.

Description

Performance enhancing additives for fuel compositions and methods of use thereof

Field of Invention:

The present invention relates to performance enhancing additives for fuel compositions, fuel compositions comprising the performance enhancing additives, and methods of use thereof.

Background and Necessity of the Invention:

Modern diesel engines with injection systems have become more energy efficient.

Accordingly, the industry needs additives that can improve the performance of fuels to reduce power loss, particularly when the fuels are used in diesel engines.

Accordingly, the present invention needs to provide performance enhancing additives for fuel compositions, fuel compositions comprising the performance enhancing additives, and methods of use thereof.

Problems to be solved by the present invention:

Accordingly, the present invention aims to provide a solution to the power loss problem of modern diesel engines.

Purpose of the invention:

Accordingly, a primary object of the present invention is to provide performance enhancing additives for fuel compositions, fuel compositions comprising the performance enhancing additives, and methods of use thereof.

Other objects and advantages of the present invention will become more apparent from the following description when understood in conjunction with embodiments which are not intended to limit the scope of the present invention.

DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS:

To provide a solution to the problem of power loss in diesel engines, the inventors of the present invention have discovered that when a blend or mixture of an acid amide and an oxidized amine is added to a fuel, the resulting fuel composition can surprisingly and unexpectedly improve engine power. It has been found that reducing losses represents an improvement in the performance of a diesel engine or fuel.

Thus, in one embodiment, the present invention provides a composition comprising (i) an acid amide (component A); and (ii) a derivative of an oxide-treated amine (component B).

Thus, in another embodiment, the present invention also provides a composition comprising (i) an acid amide (component A) for improving the performance of an engine or a fuel used in an engine by reducing the power loss of the engine; and (ii) a derivative of an oxide treated amine (component B).

Thus, in another embodiment, the present invention relates to (A) fuels used in modern engines; and (B) (i) an acid amide; and (ii) a performance enhancing additive composition comprising a mixture or blend of a derivative of an oxide treated amine.

According to one embodiment of the present invention, the acid amide (component A) is the reaction product of polyisobutylene succinic anhydride (PIBSA) and tetraethylene pentamine (TEPA).

According to one preferred embodiment of the present invention, PIBSA specifically reacts with TEPA at a temperature of less than about 100°C.

According to one of the embodiments of the present invention, the derivative of an oxide treated amine (component B) is the reaction product of an oxide and an amine.

According to one embodiment of the present invention, the oxide is selected from the group comprising ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO) and other oxides.

According to one of the embodiments of the present invention, the amine is preferably a tertiary amine, more preferably a tertiary amine containing at least one hydroxyl group in the alkyl chain, even more preferably tri-isopropanolamine (TIPA) to be.

Thus, according to one of the embodiments of the present invention, the oxide treated amine derivatives are ethylene oxide (EO) treated amine derivatives, propylene oxide (PO) treated amine derivatives, and butylene oxide (BO) treated amine derivatives. It is selected from the group comprising derivatives of amines.

According to one of the preferred embodiments of the present invention, the derivative of the oxide treated amine is obtained by any known method, preferably by reacting the amine with the oxide, taken in various weight ratios from about 0.5:4 to about 2:16 respectively, to obtain a more preferably by reacting an amine and an oxide taken in various weight ratios of from about 1:8 to about 2:16 respectively, even more preferably by reacting an amine and an oxide taken in a weight ratio of about 1:8 respectively. have.

According to one of the preferred embodiments of the present invention, the derivative of an oxide treated amine is prepared by reacting an amine with an oxide in the presence of a hydroxide or an alcoholic hydroxide, preferably potassium hydroxide.

According to one of the preferred embodiments of the present invention, the (i) acid amide (component A) of the present invention; and (ii) a derivative of an oxidized amine (component B) may be prepared by mixing or blending components A and B in any molar ratio or in any weight ratio. For example, the weight ratio of acid amide and oxide treated amine can vary from about 99:1 to about 1:99. Oxidized amines can be obtained by mixing various molar ratios of amine to oxide from about 1:1 to about 1:50 molar.

According to one of the embodiments of the present invention, the additive composition described above may further comprise a detergent (component C).

Thus, in another embodiment, the present invention provides (I) (i) an acid amide (component A); and (ii) a mixture or blend of an oxide-treated derivative of an amine (component B); and (II) a detergent (component C).

Thus, in another embodiment, the present invention also relates to (I) (i) an acid amide (component A); and (ii) a mixture or blend of an oxide-treated derivative of an amine (component B); and (II) a detergent (component C).

Thus, in another embodiment, the present invention provides a composition comprising (I) (i) an acid amide (component A); and (ii) a derivative of an oxide-treated amine (component B); (II) detergent (component C); and (III) a fuel composition comprising a fuel used in modern engines.

According to one embodiment of the present invention, the detergent is polyisobutylene succinimide (PIBSI).

According to one preferred embodiment of the present invention, polyisobutylene succinimide (PIBSI) is the reaction product of polyisobutylene succinic anhydride (PIBSA) and tetraethylene pentamine (TEPA).

According to one preferred embodiment of the present invention, PIBSA specifically reacts with TEPA at high temperatures above about 1000 °C.

According to one preferred embodiment of the present invention, PIBSA can be prepared by any known method, preferably from highly reactive polyisobutylene (HRPIB).

According to one preferred embodiment of the present invention, conventional PIBs and so-called "highly reactive" PIBs (see eg EP-B-0565285) are suitable for use in the present invention. In this context, a highly reactive PIB is defined as a PIB in which at least 50%, preferably more than 70%, of the terminal olefin double bonds are of the vinylidene type, for example the GLISSOPAL compound available from BASF.

According to a second embodiment of the present invention, the detergent (component C) may be mixed or blended with a mixture or blend of (i) an acid amide (component A) and (ii) a derivative of an oxidized amine (component B), or or, alternatively, the detergent (component C) can be mixed or blended with (i) an acid amide (component A) and (ii) a derivative of an oxide treated amine (component B) to form the composition of the present invention. can be noticed.

According to one of the preferred embodiments of the present invention, the (i) acid amide (component A) of the present invention; (ii) derivatives of oxide-treated amines (component B); and (iii) detergent (component C) may be mixed or blended in any mole ratio or any weight ratio. For example, the weight ratio of acid amide and oxide treated amine can vary from about 99:1 to about 1:99. Oxidized amines can be obtained by reacting amines with oxides in various molar ratios from about 1:1 to about 1:50 molar. Additionally, the acid amide:oxide treated amine:detergent can be mixed or blended in various weight ratios from about 1:0.1:0.1 to about 0.1:1:1.

Accordingly, in another embodiment, the present invention also relates to fuels used in engines and methods of improving the performance of engines by reducing the power loss of the engines using the performance enhancing additive compositions of the present invention.

In one exemplary embodiment, the detergent of the present invention is polyisobutylene succinimide (PIBSI), which may be prepared by methods known in the art. Preferably, PIBSI can be prepared by the following two-step reaction.

Step-1: Synthesis of polyisobutylene succinic anhydride (PIBSA) : (not inventive):

a) About 1297.5 g of commercially available highly reactive polyisobutylene (HRPIB) having a molecular weight of 750 was charged to a clean, dry four-necked flask. The temperature was raised to about 125 °C;

b) about 201.8 g of maleic anhydride was added and the resulting reaction mixture was further heated to a temperature of about 170° C. for about 2 hours;

c) the reaction mixture was further heated to about 205° C. for about 3 hours and held at the same temperature, i.e., about 205° C. for about 6 hours;

d) then the excess maleic anhydride is distilled off;

e) The reaction mixture was diluted with toluene to give PIBSA, which was found to be 85% active in toluene.

STEP-2: Synthesis of polyisobutylene succinimide (PIBSI) from PIBSA in STEP-1 - [referred to as PDA1 in the Examples] :

In toluene as obtained in step-1 above to a clean, dry four-necked flask. 85% active PIBSA About 400 g was charged and about 76.1 g of TEPA was added to it with continuous stirring at room temperature. The resulting reaction mixture is then heated to a temperature of about 140° C. to 150° C., preferably, in the case of this example, about 145-147° C., to complete the reaction to form a cyclic ring compound—PIBSI. It was held at this temperature for about 4 hours. After that, toluene was completely distilled off. The reaction mixture was diluted with a heavy aromatic solvent (HAR) (the solvent in this example is naphtha) to give a cyclic compound-PIBSI, which is:

• Average molecular weight (Mw) of about 750 Daltons as determined by Gel Permeation Chromatography (GPC);

• Nitrogen content of 7% calculated by elemental analysis; and

ㆍ Total amine value of about 133 mg KOH/g calculated by ASTM D 2074-16 method

was found to have

In one exemplary embodiment, the acid amide of the present invention is the reaction product of polyisobutylene succinic anhydride (PIBSA) and TEPA, which may be prepared by methods known in the art. Preferably, the acid amide can be prepared by the following reaction.

Step-A: Synthesis of Acid Amide (Component A) :

In a clean dry four-necked flask, to about 200 g of 85% active PIBSA in toluene obtained in step-1 above was added about 40.18 g of TEPA at room temperature under stirring. The resulting reaction mixture is then heated to a temperature of from about 60° C. to about 100° C., preferably from about 70° C. to about 90° C., and for the purposes of this example, in particular about 80° C., for up to about 7 hours, preferably was held for various times up to about 7 hours, and for the purposes of this example, in particular up to about 5 hours. This reaction can also be carried out at room temperature, but since the cyclic ring compound of step-2 - PIBSI can then be formed, and the purpose of this example is to avoid the formation of the cyclic ring compound of step-2 - PIBSI above, 100 Temperatures above °C may not be performed. Toluene was then distilled off to obtain an acid amide, which was identified as component A of the present invention. Component A (acid amide) is:

• an acid value of about 18 mg KOH/g calculated by ASTM D664-16 method;

• Nitrogen content of 5% calculated by elemental analysis; and

ㆍ Total amine value of about 123 mg KOH/g calculated by ASTM D 2074-16 method

was found to have

Step-B: Preparation of PO-TIPA Derivative (Component B):

About 437 gm of TIPA was charged into an autoclave to which about 7.5 gm of potassium hydroxide (KOH) was added, about 1062.5 gm of PO was added, and the resulting reaction mixture was heated to a temperature of about 130°C. The temperature of the resulting reaction mixture was maintained at about 130° C. for about 2-3 hours to form a PO-TIPO derivative. The reaction mixture was cooled to room temperature (RT) and the PO-TIPA derivative was isolated, which was identified as Component B of the present invention. Component B (PO-TIPO derivative) is:

• Nitrogen content of 3% calculated by elemental analysis; and

ㆍ Total amine value of about 91 mg KOH/g calculated by ASTM D 2074-16 method

was found to have

Preparation of the mixture or blend of component A and component B: - [referred to as PDA7 in the examples]:

In one exemplary embodiment of the present invention, a mixture or blend of component A and component B can be prepared by the following process. [referred to as PDA7 in the examples]

About 150 g of component A (acid amide) obtained in step-A above was mixed with about 95 g of component B [PO-TIPA derivative obtained from TIPA:PO taken in a weight ratio of about 1:8 in step-B above] The addition was added to a clean, dry four-necked flask, and the resulting reaction mixture was heated to a temperature of about 78-80° C. for about 4 hours. Even heating their reaction mixture to a temperature of about 78-80° C. for about 4 hours resulted in the formation of two separate layers confirming that no chemical reaction occurred between component A and component B of the present invention. Observed.

Analysis of these two separate layers confirmed that mixing and heating of components A and B did not result in the formation of a quaternary salt, and thus no chemical reaction between components A and B of the present invention. .

For one of the exemplary embodiments of the present invention, the two separate layers thus formed are diluted with toluene to give 50% activity, resulting in a homogenized monolayer, i.e., a mixture or blend of the present invention, component A and components A mixture or blend of B was formed.

Analysis of mixtures or blends of 50% Active Ingredient A and 50% Active Ingredient B:

ㆍAcid value of about 5 mg KOH/g when calculated by ASTM D664-16 method;

• 3% nitrogen content calculated by elemental analysis; and

ㆍCalculated by ASTM D 2074-16, total amine value of about 65 mg KOH/g.

Abbreviation:

In the present invention, the following abbreviations have been used:

• TIPA is tri-isopropanolamine;

• PO-TIPA is the propylene oxide (PO) derivative of TIPA;

• 750 PIBSI is a polyisobutylene succinimide with an average molecular weight (M _w ) of 750 Daltons;

• HRPIB is a highly reactive polyisobutylene;

• TEPA is tetraethylene pentamine;

• PIBSA is polyisobutylene succinic anhydride;

• HAR is a heavy aromatic solvent.

Accordingly, in a first embodiment, the performance enhancing additive composition of the present invention comprises (i) an acid amide (ie, the reaction product of PIBSA & TEPA, ie, component A of Step A); and (ii) an oxide treated derivative of TIPA, such as a PO-TIPA derivative (ie the product of TIPA & PO, ie component B of Step-B).

Accordingly, in a second embodiment, the performance enhancing additive composition of the present invention comprises (i) an acid amide (ie, the reaction product of PIBSA & TEPA, ie, component A of Step A); and (ii) an oxide treated derivative of TIPA, such as a PO-TIPA derivative (ie the product of TIPA & PO, ie component B of Step-B); and (iii) a mixture/blend further comprising PIBSI (Component C) as a detergent.

Further embodiments of the invention will be apparent from the appended examples, which are illustrative and do not limit the scope of the invention.

Example:

Various diesel fuel compositions were prepared to evaluate the efficiency of presently provided additive compositions using commercially available reference fuels suitable for the test methods used. For example, for the CEC-F-98-08 test method, a commercially available CEC RF-79-07 reference fuel may be used. This reference fuel has a cetane number of about 52 to about 54 as measured by the EN ISO 5165 method, a density of about 833 to about 837 Kg/m ³ at 15° C. as measured by the EN ISO 12185 method, and an EN ISO It is known to have a flash point of at least about 62° C. as measured by the 2719 method and a viscosity of about 2.300 to about 3.300 mm ² /s at 40° C. as measured by the EN ISO 3104 method. It is also possible to use commercially available CEC RF 06 03 standard fuel. This reference fuel has a cetane number of about 52 to about 54 as measured by the EN ISO 5165-98 method, a density of about 833 to about 837 Kg/m ³ at 15° C. as measured by the EN ISO 3675-98 method, and an EN ISO It is known to have a flash point of at least about 55° C. as measured by the 22719 method and a viscosity of about 2.3 to about 3.3 mm ² /s at 40° C. as measured by the EN ISO 3104 method. To these exemplary compositions, about 1 ppm of zinc was added as zinc neodecanoate. The resulting composition was tested by method CEC-F-98-08. For these experiments, CEC RF-79-07 reference fuel, a standard reference fuel specified by the Coordinating European Council (CEC) for the CEC-F-98-08 engine test method, was used. It may be noted that the scope of the present invention is not limited by the test method or by the reference fuel used in the test method.

In the following exemplary composition, PDA1 and PDA7 are the same as previously described herein.

Table 1 experiment number fuel composition total pure
Additive (ppm) % Power
Loss One. Base fuel RF79, no additives 4.7 2. Base fuel RF79 with PDA1 of 74 ppm 74 2.3 3. Base fuel RF79 with PDA1 at 31 ppm and PDA7 at 25 ppm 56 2.3 4. Base fuel RF79 with 100 ppm of PDA7 100 0.9 5. Base fuel RF79 with PDA7 at 50 ppm and PDA1 at 31 ppm 81 0.7 6. Base fuel RF79 with PDA7 at 50 ppm and PDA1 at 62 ppm 112 0.5

As can be observed from the experimental results in Table 1 above, the base fuel with 74 ppm of additive PDA1 exhibits a power loss of 2.3%, and the base fuel with 100 ppm of additive PDA7 exhibits substantially a power loss of 0.9%. shows a lower % power loss, where the addition of detergent to PDA1, ie additive PDA7, results in a more substantial reduction in % power loss to 0.7% or 0.5%. Thus, the composition of the present invention exhibits a surprising and unexpected technical advantage, i.e., a synergistic effect.

As can be observed from the experimental results in Table 1 above, PDA7 or the composition of the present invention comprising PDA7 and PDA1 was compared with a blank sample and a sample made of a prior art additive, that is, PDA1 without the additive composition of the present invention. Thus, it was shown that the performance was improved by reducing the % power loss.

Claims (11)

(i) acid amides; and
(ii) a performance enhancing additive composition comprising a mixture or blend of derivatives of an oxide treated amine;
The acid amide consists of the reaction product of polyisobutylene succinic anhydride (PIBSA) and tetraethylene pentamine (TEPA);
The oxide-treated amine derivative consists of the reaction product of an oxide and an amine;
the amine consists of tri-isopropanolamine (TIPA);
the oxide consists of propylene oxide (PO);
Wherein the oxide-treated derivative of amine consists of a propylene oxide-treated derivative of tri-isopropanolamine (PO-TIPA).
The composition of claim 1 , wherein the composition further comprises a detergent.
3. The composition of claim 2, wherein the detergent is polyisobutylene succinimide (PIBSI).
A performance enhancing additive composition according to any one of claims 1 to 3 for improving the performance of an engine or a fuel used in an engine by reducing the power loss of the engine.
A method for improving the performance of an engine or a fuel used in an engine by reducing the power loss of the engine, the method comprising using the performance enhancing additive composition according to any one of claims 1 to 3 for the engine or engine. A method comprising the step of adding to the fuel to be.
(A) engine fuel; and
(B) a fuel composition comprising the performance enhancing additive composition according to any one of claims 1 to 3.
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